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Method for high value utilization of Fischer-Tropsch synthesis tail gas

A Fischer-Tropsch synthesis, high-value technology, applied in the preparation of liquid hydrocarbon mixtures, organic chemistry, lubricating compositions, etc., can solve the problems of high ethylene prices, achieve easy industrialization, increase product added value, and operate convenient effect

Active Publication Date: 2014-03-26
SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Ethylene oligomerization is the main method for producing α-olefins. At present, ethylene is mainly derived from petrochemicals. The rise in oil prices has led to high ethylene prices. Although the coal-to-olefins process has alleviated the pressure of ethylene shortage to a certain extent, it has Still can't fundamentally solve the problem

Method used

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  • Method for high value utilization of Fischer-Tropsch synthesis tail gas

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Experimental program
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Effect test

Embodiment 1

[0034] Fischer-Tropsch reactor 1 adopts a tubular fixed-bed reactor. The inner diameter of the reactor shell is 200mm, the reactor tube length is 12m, and the tube diameter is Ф38x3mm. There are 7 tubes in total, arranged in an equilateral triangle, and the tube center distance is 48mm. The lower end of the reaction tube is equipped with a plugging spring, and the catalyst of each reaction tube can be discharged separately. The bottom of the bed is filled with Ф6mm ceramic balls for about 200mm, the top of the bed is filled with Ф6mm ceramic balls for about 200mm, the catalyst filling height is 11m, and the loading capacity is about 60L.

[0035] The catalyst is Co / ZrO 2 Catalyst, the catalyst is cylindrical after molding, d=4mm, h=5mm, density 0.87x10 3 Kg / m 3 , the porosity is about 0.3. The catalyst is prepared according to Chinese patent CN1398669: Co(NO 3 ) 2 ·6H 2 O, ZrOCl 2 and Mn(NO 3 ) 2 The mixed solution, the preparation concentration is 0.2M Na 2 CO 3 Sol...

Embodiment 2

[0046] Fischer-Tropsch reactor 1 adopts a slurry bed reactor, the inner diameter of the reactor shell is 1m, and the reactor volume is 1.2m 3 , the catalyst loading is about 25L, and the density is 0.8x10 3 Kg / m 3 . Catalyst selects Fe / Mn / Ca / K (100 / 50 / 11 / 4.5) catalyst, prepares according to the method described in patent CN1463794: Weigh Fe(NO 3 ) 3 9H 2 O194.07g, Ca(NO 3 ) 4 4H 2 O12.5g and concentration of 50% Mn(NO 3 ) 2 85.99g of the solution was prepared with deionized water to make a mixed solution with a total concentration of 0.3mol / L, and heated in a water bath at 50°C; a 0.5mol / L ammonia solution was prepared, added to the salt solution, stirred and precipitated, and allowed to stand for 12 hours. Suction filtration, washing and drying. Grind the dried filter cake finely, impregnate it with 16ml of potassium carbonate with a concentration of 0.91mol / L for 3h, dry it; then roast it at 500°C for 5h to obtain the final catalyst.

[0047] 48Nm from purificatio...

Embodiment 3

[0056] Fischer-Tropsch reactor 1 adopts a fixed fluidized bed reactor with a main pipe diameter of 0.5m and a height of 10m. The catalyst loading is about 50L and the density is 1.0x10 3 Kg / m 3 .

[0057] The catalyst is 16.8Co 3 o 4 / 0.2RuO 2 / Al 2 o 3 Catalyst, prepare catalyst according to the method described in Chinese patent CN102962066A: prepare a certain amount of 1mol / L aluminum sulfate aqueous solution, drop into 10mlNaOH, keep the water bath temperature as 40 ℃, hold time 180min, account for 0.2 (wt) of final catalyst by ruthenium oxide % Weighing RuCl 3 ·3H 2 O was added to the solution, peptizer H was added 2 SO 4 , stirred and refluxed at a microwave power of 50W until a transparent sol was maintained for 6h, and then aged at room temperature for 24h to obtain a gel. After drying at 50°C for 2 hours, place it in a microwave oven, heat up to 550°C for 12 hours at 2°C / min, and bake for 12 hours to prepare a catalyst carrier. Weigh Co(NO 3 ) 2 ·6H 2 O,...

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Abstract

The invention relates to a method for high value utilization of Fischer-Tropsch synthesis tail gas. The method comprises that: Fischer-Tropsch synthesis reaction products enter a first heat exchanger in a gas phase form so as to be subjected to heat exchange, and gas-liquid separation is performed to obtain hard wax; heat exchange is performed through a second heat exchanger, and gas-liquid separation is performed to obtain soft wax; and a water cooling device is adopted to separate heavy oil, an ammonia cooling device is adopted to separate to obtain light oil and synthesis water, one part of the non-condensable tail gas is adopted as the circulation gas, is pre-heated through the second heat exchanger and the first heat exchanger, and then enters the Fischer-Tropsch synthesis reactor, the other part is adopted as the relief gas so as to carry out low carbon alkane dehydrogenation to produce low carbon olefins, the low carbon olefins are subjected to aromatization to produce BTX or are subjected to polymerization to produce terminal olefins, and the lubricating oil poly alpha olefin is further synthesized. The method has advantages of low production cost, high product price, and good quality.

Description

technical field [0001] The invention relates to a method for high-value utilization of Fischer-Tropsch synthesis tail gas. technical background [0002] Fischer-Tropsch synthesis is a chemical process that converts synthesis gas into higher hydrocarbons, and is one of the most important ways to efficiently convert and utilize non-petroleum carbon resources (natural gas, coal, residual oil, and biomass, etc.). The Fischer-Tropsch synthesis reaction can effectively alleviate the contradiction between supply and demand of oil products to a certain extent, and by virtue of its ability to reduce CO in the process of coal utilization 2 The advantages of capture and utilization of pollutants and other pollutants and the continuous improvement of energy conversion efficiency have attracted increasing attention. [0003] The purge gas of the Fischer-Tropsch synthesis reaction accounts for about 3% to 8% of the fresh synthesis gas, and its main components are CO, H 2 , N 2 And low-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10G2/00C10G73/44C07C15/04C07C15/06C07C15/08C10M107/02
Inventor 李德宝刘岩侯博贾丽涛陈从标王俊刚
Owner SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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